Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
  • C08L89/04—Products derived from waste materials, e.g. horn, hoof or hair
  • C08L89/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin, e.g. gelatin
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/02—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with cellulose derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
  • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
  • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2203/00—Macromolecular materials of the coating layers
  • D06N2203/02—Natural macromolecular compounds or derivatives thereof
  • D06N2203/024—Polysaccharides or derivatives thereof
  • D06N2203/026—Cellulose or derivatives thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2205/00—Condition, form or state of the materials
  • D06N2205/14—Fibrous additives or fillers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2211/00—Specially adapted uses
  • D06N2211/12—Decorative or sun protection articles
  • D06N2211/28—Artificial leather

Definitions

• the present invention relates to a composition, a sheet-shaped molded product, artificial leather, and a method for producing a sheet-shaped molded product.
• Natural leather or synthetic leather is widely used as a fashion material and an interior material because it has a texture and durability comparable to that of natural leather.
• natural leather-like artificial leather mainly composed of fiber entanglements mainly composed of ultrafine fibers and polymer elastic bodies has excellent characteristics in comparison with natural leather such as high durability and uniformity of quality. It is used not only as a material for clothing, but also in various fields such as vehicle interior materials, interiors, shoes and clothing.
• Patent Document 1 describes a heat-molded sheet having synthetic leather or artificial leather containing fine powder of natural organic matter ([Claim 1] [Claim 4]), and natural leather as a natural organic matter.
• One or more selected from the group consisting of powder, silk powder and cellulose powder is described ([Claim 2]).
• thermoforming sheet described in Patent Document 1 When the present inventors examined the thermoforming sheet described in Patent Document 1, it was clarified that there is room for improvement in the degree of matteness of the leather surface when used as synthetic leather or artificial leather. bottom.
• the present invention provides a composition, a sheet-shaped molded body, an artificial leather, and a method for producing a sheet-shaped molded body, which can realize an excellent matte-like leather surface when used as synthetic leather or artificial leather. That is the issue.
• the present inventors have made excellent mats when a composition containing a polypeptide, a fibrous substance other than the polypeptide and a plasticizer is used as synthetic leather or artificial leather.
• a composition containing a polypeptide, a fibrous substance other than the polypeptide and a plasticizer is used as synthetic leather or artificial leather.
• a toned leather surface we have found that it is possible to realize a toned leather surface, and completed the present invention. That is, the present inventors have found that the above-mentioned problems can be achieved by the following configurations.
• a composition used for synthetic leather or artificial leather which contains a polypeptide, a fibrous substance other than the polypeptide, and a plasticizer.
• the cross-linking agent is a triazine-based compound or a vinyl sulfone-based compound.
• the composition according to any one of [1] to [4], wherein the fibrous substance has an average fiber length of 2 to 500 ⁇ m.
• the polypeptide contains a genetically modified protein.
• a coating step of applying the composition according to any one of [1] to [10] to form a coating film and A method for producing a sheet-shaped molded product, comprising a drying step of drying the coating film to form a sheet-shaped molded product after the coating step.
• compositions a sheet-shaped molded body, an artificial leather, and a method for producing a sheet-shaped molded body, which can realize an excellent matte-like leather surface when used as synthetic leather or artificial leather. be able to.
• the present invention will be described in detail.
• the description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
• the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• a substance corresponding to each component may be used alone or in combination of two or more.
• the content of the component means the total content of the substances used in combination unless otherwise specified.
• composition of the present invention is a composition used for synthetic leather or artificial leather containing a polypeptide, a fibrous substance other than the polypeptide, and a plasticizer.
• a composition containing a polypeptide, a fibrous substance other than a polypeptide, and a plasticizer realizes an excellent matte leather surface when used as synthetic leather or artificial leather. Can be done. The reason for this effect is not clear in detail, but the present inventors speculate as follows. First, polypeptides are considered to be a substitute for dermis (collagen), which is a raw material for leather. Then, by blending a plasticizer, a texture close to that of natural leather can be obtained, and by blending a fibrous substance, the fibrous substance aggregates or precipitates near the surface layer when synthetic leather or artificial leather is produced.
• the excellent matte-like leather surface could be realized because the surface layer was dried slowly and the generation of luster was suppressed.
• the polypeptide, fibrous substance and plasticizer contained in the sheet-shaped molded product of the present invention will be described in detail.
• the polypeptide contained in the composition of the present invention is not particularly limited as long as it can form a film by coating.
• the weight average molecular weight of the polypeptide is preferably 20,000 to 1,000,000, more preferably 25,000 to 95,000.
• the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC) method.
• polypeptide examples include gelatin, collagen, protamine, polyarginine, or a genetically modified product having an amino acid sequence derived from a partial amino acid sequence thereof. These may be used alone or in combination of two or more.
• gelatin and a genetically modified protein may be used in combination.
• gelatin, collagen or genetically modified proteins are preferred.
• the origin of gelatin or collagen is not particularly limited, but is preferably bovine, pig, mouse, or rat. More preferably, it is a cow. Further, one animal species may be used as the origin of collagen, or two or more species may be combined.
• the polypeptide that can be used in the present invention may be pre-crosslinked or may not be pre-crosslinked, but a pre-crosslinked polypeptide is preferable.
• the pre-crosslinking is to crosslink the polypeptide in advance before mixing with a fibrous substance other than the polypeptide, a plasticizer, and any cross-linking agent.
• Pre-crosslinking methods include thermal cross-linking, chemical cross-linking, cross-linking with aldehydes (eg, formaldehyde, glutaaldehyde, etc.), cross-linking with condensing agents (carbodiimide, cyanamide, etc.), enzyme cross-linking, photocross-linking, UV cross-linking, hydrophobic mutual.
• Known methods such as action, hydrogen bonding, and ionic interaction can be used.
• Examples of the photocrosslinking include light irradiation on a polymer having a photoreactive group introduced, or light irradiation in the presence of a photosensitizer.
• Examples of the photoreactive group include a cinnamyl group, a coumarin group, a dithiocarbamyl group, a xanthene dye, and a kanfaquinone.
• the enzyme When cross-linking with an enzyme, the enzyme is not particularly limited as long as it has a cross-linking action between polypeptides, and examples thereof include transglutaminase and laccase.
• Specific examples of the protein enzymatically cross-linked with transglutaminase are not particularly limited as long as it is a protein having a lysine residue and a glutamine residue.
• the transglutaminase may be derived from a mammal or a microorganism.
• the Activa series manufactured by Ajinomoto Co., Inc. a transglutaminase derived from a mammal sold as a reagent, for example, Human-derived blood coagulation factors (Factor XIIIa, Haematologic Technologies, Inc.) such as guinea pig liver-derived transglutaminase, goat-derived transglutaminase, and rabbit-derived transglutaminase manufactured by Oriental Yeast Co., Ltd., Upstate USA Inc., Biodesign International, etc. .Company) and so on.
• Human-derived blood coagulation factors Factor XIIIa, Haematologic Technologies, Inc.
• guinea pig liver-derived transglutaminase goat-derived transglutaminase
• Pre-crosslinking a polypeptide has two processes: a process of mixing a solution of the polypeptide and a cross-linking agent, and a process of reacting a uniform solution thereof.
• the mixing temperature when treating the polypeptide with a cross-linking agent is not particularly limited as long as the solution can be uniformly stirred, but is preferably 0 ° C to 40 ° C, more preferably 0 ° C to 30 ° C. It is more preferably 3 ° C to 25 ° C, more preferably 3 ° C to 15 ° C, still more preferably 3 ° C to 10 ° C, and particularly preferably 3 ° C to 7 ° C.
• the temperature can be raised after stirring the polypeptide and the cross-linking agent.
• the reaction temperature is not particularly limited as long as crosslinking proceeds, but is substantially 0 ° C. to 60 ° C., more preferably 0 ° C. to 40 ° C., more preferably 0 ° C. to 40 ° C. in consideration of denaturation and decomposition of the polypeptide. Is 3 ° C to 25 ° C, more preferably 3 ° C to 15 ° C, still more preferably 3 ° C to 10 ° C, and particularly preferably 3 ° C to 7 ° C.
• the above-mentioned polypeptide preferably contains a genetically modified protein because the texture can be adjusted by using a protein having a uniform sequence.
• a genetically modified protein is a polypeptide having an amino acid sequence derived from an organism produced by a genetically modified technique.
• the amino acid sequence of the genetically modified protein is not particularly limited, but collagen, gelatin, or a variant thereof is preferable because it can be used as a substitute for the dermis (collagen) which is a raw material of leather.
• the genetically modified protein may contain a single sequence of naturally occurring collagen, or may contain a plurality of bound proteins.
• the recombinant protein may have a repeat of the sequence represented by Gly-XY, which is characteristic of collagen (hereinafter, also abbreviated as "GXY sequence").
• GXY sequence is characteristic of collagen
• the plurality of Gly-XY may be the same or different from each other.
• Gly-XY Gly represents glycine and X and Y represent any amino acid (preferably any amino acid other than glycine).
• the GXY sequence characteristic of collagen is a very specific partial structure in the amino acid composition and sequence of gelatin / collagen as compared with other proteins. In this part, glycine occupies about one-third of the whole, and the amino acid sequence is one in three repetitions.
• the amino acids represented by X and Y are rich in imino acids (proline, oxyproline) and preferably account for 10% to 45% of the total genetically modified protein.
• the genetically modified protein preferably has a GXY sequence containing 80% or more, more preferably 95% or more, and most preferably 99% or more of the amino acids in the sequence.
• the organism from which the genetically modified protein is derived is not particularly limited, but is preferably mammals and reptiles. Species derived from these recombinant proteins are not limited to extant species and may include extinct species. In addition, these genetically modified protein-derived organisms may be used alone or in combination of two or more. Existing species include elephants, crocodile, hippo, sai, armadillo, tiger, lion, leopard, cheetah, whale, wolf, shark, ray, lizard, panda, iguana, jaguar, jugon, bear, gorilla, lizard, snake, ostrich. And so on.
• Extinct species include mammoths, naumann elephants, mastodons, saber tigers, tyrannosaurus, triceratops, stegosaurus, pteranodons, and urvogels.
• the genetically modified protein that can be used in the present invention can be produced by a genetically modified technique known to those skilled in the art, and is produced according to the method described in, for example, EP1014176A2, US6992172, WO2004 / 85473, WO2008 / 103041 and the like. be able to. Specifically, a gene encoding the amino acid sequence of a predetermined recombinant protein is obtained, this is incorporated into an expression vector to prepare a recombinant expression vector, and this is introduced into an appropriate host to prepare a transformant. do. By culturing the obtained transformant in an appropriate medium, a genetically modified protein is produced. Therefore, by recovering the genetically modified protein produced from the culture, the genetically modified protein that can be used in the present invention can be produced. Can be prepared.
• the content of the polypeptide is preferably 40 to 95% by mass, more preferably 45 to 90% by mass, and 50 to 85% by mass with respect to the total solid content of the composition. It is more preferably by mass%.
• the fibrous substance contained in the composition of the present invention is not particularly limited as long as it is a substance whose length is 100 times or more the average value of the outer diameter.
• the average fiber diameter of the fibrous substance is preferably 1 to 400 nm, more preferably 30 to 300 nm, because a more excellent matte leather surface can be realized. It is more preferably 40 to 200 nm.
• the average fiber diameter of the fibrous material is obtained by measuring the fiber diameter of an arbitrary number (for example, 20) of the fibrous material by electron microscope observation and as an arithmetic average value of the obtained measured values.
• the average fiber length of the fibrous substance is preferably 2 to 500 ⁇ m, more preferably 4 to 400 ⁇ m, for the reason that a more excellent matte leather surface can be realized. It is more preferably 6 to 300 ⁇ m. Further, the average fiber length of the fibrous substance may be 10 ⁇ m or more, 20 ⁇ m or more, 50 ⁇ m or more, or 80 ⁇ m or more. The average fiber length of the fibrous substance may be 250 ⁇ m or less, 200 ⁇ m or less, 180 ⁇ m or less, or 150 ⁇ m or less.
• the average fiber length of the fibrous material is obtained by measuring the fiber length of an arbitrary number (for example, 20) of the fibrous material by electron microscope observation and as an arithmetic average value of the obtained measured values.
• the aspect ratio (fiber length / fiber diameter) of the fibrous substance is preferably 100 or more, preferably 100 to 3000, for the reason that a more excellent matte leather surface can be realized. More preferably, 150 to 2000 is even more preferable. Further, the aspect ratio of the fibrous substance may be 200 or more, 300 or more, 400 or more, 500 or more, or 600 or more. Further, the aspect ratio of the fibrous substance may be 1800 or less, 1500 or less, 1300 or less, or 1000 or less.
• the fibrous substance examples include nanofibers.
• the nanofibers may contain fibers having a fiber diameter of 1 ⁇ m or more as long as the average fiber diameter is less than 1 ⁇ m.
• Specific examples of the nanofibers include cellulose nanofibers, chitin nanofibers, chitosan nanofibers, carbon nanofibers, glass nanofibers, metal oxide nanofibers, synthetic resin nanofibers, and aramid nanofibers. Can be mentioned. Of these, cellulose nanofibers are preferable because they can realize a more excellent matte leather surface.
• cellulose nanofibers include plant-derived fibers contained in wood, bamboo, hemp, jute, kenaf, cotton, beet pulp, potato pulp, agricultural waste, cloth, paper, etc., and these are used alone. Alternatively, two or more kinds may be used in combination. Examples of the wood include sitka spruce, sugi, cypress, eucalyptus, acacia and the like. Examples of the paper include deinked used paper, corrugated cardboard used paper, magazines, copy paper and the like. Examples of the pulp include chemical pulp (craft pulp (KP), sulfite pulp (SP)) and semi-chemical pulp (SCP) obtained by pulping plant raw materials chemically or mechanically or in combination thereof. , Semi-grand pulp (CGP), chemi-mechanical pulp (CMP), crushed wood pulp (GP), refiner mechanical pulp (RMP), thermomechanical pulp (TMP), chemi-thermomechanical pulp (CTMP) and the like.
• wood sitka spruce, sugi, cy
• Cellulose nanofibers may be chemically modified and / or physically modified to enhance their functionality.
• the chemical modifications include, for example, a carboxy group, an acetyl group, a sulfate group, a sulfonic acid group, an acryloyl group, a methacryloyl group, a propionyl group, a propioloyl group, a butyryl group, a 2-butyryl group, a pentanoyl group, a hexanoyl group and a heptanoyle.
• Achill group such as a group, an octanoyl group, a nonanoyl group, a decanoyle group, an undecanoyl group, a dodecanoyl group, a myritoyl group, a palmitoyl group, a stearoyl group, a pivaloyl group, a benzoyl group, a naphthoyl group, a nicotinoyle group, an isonicotinoyle group, a floyl group, and a cinnamoyl group.
• 2-methacryloyloxyethyl isocyanoyl group and other isocyanate groups methyl group, ethyl group, propyl group, 2-propyl group, butyl group, 2-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, Examples thereof include addition of an alkyl group such as an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a myristyl group, a palmityl group and a stearyl group, an oxylan group, an oxetane group, a thiilan group and a thietan group.
• an alkyl group such as an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a myristyl group
• the usual method can be adopted for chemical modification. That is, it can be chemically modified by reacting cellulose with a chemical modifying agent. If necessary, a solvent, a catalyst may be used, or heating, depressurization, or the like may be performed.
• a chemical modifying agent include cyclic ethers such as acid, acid anhydride, alcohol, halogenating reagent, alcohol, isocyanato, alkoxysilane, and oxylane (epoxy). These may be used alone or in combination of two or more.
• the acid include acetic acid, acrylic acid, methacrylic acid, propionic acid, butanoic acid, 2-butanoic acid, pentanic acid and the like.
• the chemical modification it is preferable to wash thoroughly with water in order to terminate the reaction. Residual unreacted chemical modifiers can cause coloration later or cause problems when compounded with the resin. It is preferable to wash thoroughly with water and then replace with an organic solvent such as alcohol. In this case, the cellulose is replaced by immersing it in an organic solvent such as alcohol.
• metal or ceramic raw materials are vapor-deposited by vacuum, ion plating, sputtering, or other physical vapor deposition methods (PVD method), chemical vapor deposition methods (CVD method), electroless plating, electrolytic plating, or other plating methods.
• PVD method physical vapor deposition methods
• CVD method chemical vapor deposition methods
• electroless plating electrolytic plating, or other plating methods.
• surface coating There is a method of surface coating.
• the method for adjusting the average fiber diameter of the cellulose nanofibers is not particularly limited, but for example, in the mechanical crushing method, it can be adjusted by the treatment time and the number of times of the ultra-high pressure homogenizer or grinder used, and it is a chemical crushing method. Then, adjust the type of oxidizing agent (for example, sodium hypochlorite), the concentration of the catalyst (for example, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) catalyst, etc.), the reaction time, etc. Is possible.
• the type of oxidizing agent for example, sodium hypochlorite
• concentration of the catalyst for example, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) catalyst, etc.
• the method for preparing the cellulose nanofibers is not particularly limited, and a method of mechanically or chemically crushing the cellulose nanofibers is preferable.
• a method of mechanically crushing for example, an aqueous suspension or slurry of a cellulose fiber-containing material is mechanically crushed or beaten by a refiner, a high-pressure homogenizer, a grinder, a uniaxial or multiaxial kneader, a bead mill or the like. This includes a method of defibrating.
• Japanese Patent No. 550842 Japanese Patent No. 5283050
• Japanese Patent No. 5207246 Japanese Patent No. 5170193, Japanese Patent No. 5170153
• Japanese Patent No. 4845129 Japanese Patent No. Examples thereof include Japanese Patent No. 4766484, Japanese Patent No. 4724814, Japanese Patent No. 472186, Japanese Patent No. 4428521, International Publication No. 11/068023, Japanese Patent No. 5477265, Japanese Patent Application Laid-Open No. 2014-84434, and the like.
• a method of chemically crushing for example, a cellulosic raw material is oxidized with an oxidizing agent in the presence of an N-oxyl compound and a bromide and / or an iodide, and further oxidized cellulose is obtained. It can be produced by wet atomization treatment, defibration, and nanofiber formation.
• the content of the fibrous compound is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, based on the total mass of the solid content of the composition. It is preferably 0.2 to 5% by mass, more preferably 0.2 to 5% by mass.
• the plasticizer contained in the composition of the present invention is not particularly limited.
• a hydrophilic plasticizer may be used, or a hydrophobic plasticizer may be used.
• Specific examples of the hydrophilic plasticizer include, for example. Polyhydric alcohols such as glycerol (glycerin), diglycerol, triglycerol, polyglycerol (eg, tetraglycerol, hexaglycerol, decaglycerol, or mixtures thereof), polyethylene glycol, polypropylene glycol, mannitol, sorbitol, pentaerythritol, etc.
• Sugar eg, sucrose, coupling sugar, fructo-oligosaccharide, palatinose, etc.
• starch sugar eg, glucose, maltose, powdered candy, water candy, isomerized sugar (fructose), etc.
• lactose eg, lactose, isomerized lactose (eg, lactose, isomerized lactose) Lactulose
• reduced lactose lactose (lactitol, etc.)
• honey sugar alcohols (eg, sorbitol, mannitol, reduced maltose syrup (marttoll), reduced starch saccharified product, xylitol, reduced palatinose, erythritol, etc.); Be done.
• hydrophobic plasticizer examples include phthalic acid diesters such as dibutyl phthalate and diheptyl phthalate; Aliphatic dibasic acid esters such as butyl glycol adipate and dibutyl sebacate; Epoxidized triglycerides such as epoxidized soybean oil; Phosphate esters such as tritryl phosphate, trioctyl phosphate, tritrischlorethyl phosphate; Benzoic acid esters such as benzyl benzoate; and the like. These plasticizers may be used alone or in combination of two or more.
• the above-mentioned plasticizer is preferably polyhydric alcohols because a flexible and textured surface can be obtained, and among them, a flexible and textured surface can be obtained and excellent in water resistance. For this reason, it is more preferably at least one of diglycerol and triglycerol, and even more preferably diglycerol.
• the molecular weight of the plasticizer is preferably 90 to 1100, more preferably 160 to 280, from the viewpoint of processability and handleability.
• the content of the plasticizer is preferably 0.5 to 45% by mass, more preferably 2 to 40% by mass, based on the total mass of the solid content of the composition. It is more preferably to 37% by mass.
• the composition of the present invention preferably contains a cross-linking agent because a leather surface having good durability and water resistance can be obtained.
• a cross-linking agent include a tanning agent, an isocyanate-based compound, an oxazoline-based compound, a carbodiimide compound, an epoxy-based compound, a triazine-based compound, an aldehyde-based compound, a vinyl sulfone-based compound, and a calcium phosphate-based compound.
• a tanning agent, a triazine-based compound, or a vinyl sulfone-based compound is preferable, and a triazine-based compound or a vinyl sulfone-based compound is more preferable from the viewpoint of water resistance.
• tanning agents are plant tanning based on tannins as active crosslinkers, inorganic tanning with various polyvalent metal salts, especially salts of chromium, aluminum, iron, or zirconium, and "Sintang (Sintang).
• synthetic tanning called "syntans)
• the tannin may be a natural tannin or a synthetic tannin.
• Shintan is a replacement that is an active tanning agent that can tan leather when used as a single tanning agent (eg, by reacting with collagen at two or more sites to form crosslinks). Includes cintan and auxiliary tanning that is not essentially an active tanning agent but is added to other tanning to alter the characteristics of the leather.
• Auxiliary sintan may be absorbed by leather or may react with collagen only in part.
• Sintang includes, for example, phenol and / or aryl sulfonates, as well as various polymers and copolymers such as those obtained by condensing formaldehyde with acrylate, methacrylate, acrylamide and / or acrylonitrile homopolymers and copolymers.
• Formaldehyde itself and dialdehydes eg glutaraldehyde
• the vinyl sulfone compound is a compound having a vinyl sulfone group. Further, since the vinyl sulfone compound is crosslinked by a covalent bond, the water resistance becomes good as described above.
• Examples of the vinyl sulfone compound include 1,3-bis (vinylsulfonylacetamide) propane and 1,2-bis (vinylsulfonylacetamide) ethane, and among them, 1,3-bis (vinylsulfonylacetamide). Propane is preferred. Further, the vinyl sulfone compound may be used alone or in combination of two or more, but it is preferably used alone.
• the triazine-based compound is a compound having a 1,3,5-triazine skeleton. Further, since the triazine compound is crosslinked by a covalent bond, the water resistance becomes good as described above.
• a chlorotriazine compound having an active halogen is preferable.
• the triazine-based compound include 2,4-dichloro-6-hydroxy-1,3,5-triazine monosodium 2,4,6-trichloro-1,3,5-triazine, among which 2, 4-Dichloro-6-hydroxy-1,3,5-triazine monosodium is preferred.
• the triazine-based compound may be used alone or in combination of two or more, but it is preferably used alone.
• the content of the cross-linking agent is preferably 0.5 to 20% by mass, preferably 1 to 15% by mass, based on the total mass of the solid content of the composition. Is more preferable, and 1.5 to 10% by mass is further preferable.
• the composition of the present invention preferably contains a solvent because it can be applied to the surface of various substrates to form the composition.
• the solvent is not particularly limited, and water, an organic solvent, and a mixed solvent in which these are combined can be used, but it is preferable to use water.
• the content of the organic solvent is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, based on the total mass of the solvent.
• Organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, phenylethyl alcohol, capryl alcohol, lauryl alcohol, and Alcohol-based solvents such as myristyl alcohol; methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, ethylene.
• Glycol ether solvents such as glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, and dipropylene glycol monobutyl ether; 10% denatonium benzoate alcohol solution, geraniol, octaacetylated sucrose, Hydrophilic solvents such as blucine, linalol, linaryl acetate, and acetic acid;
• composition of the present invention may contain other additives such as fats and oils, antibacterial agents, dyes, pigments and fragrances.
• additives such as fats and oils, antibacterial agents, dyes, pigments and fragrances.
• carbon black is mentioned as a kind of pigment.
• the sheet-shaped molded product of the present invention is a sheet-shaped molded product formed by using the composition of the present invention described above. That is, the sheet-shaped molded product of the present invention contains the polypeptide, the fibrous substance other than the polypeptide, and the plasticizer contained in the composition of the present invention described above.
• the composition of the present invention contains a cross-linking agent
• the polypeptide contained in the sheet-shaped molded product is a polypeptide in which a part or all of the polypeptide contained in the composition of the present invention is cross-linked. It is preferable to have.
• the arithmetic average roughness (hereinafter, also abbreviated as “Ra”) of the surface of the sheet-shaped molded product is 2.0 to 15 ⁇ m for the reason that a more excellent matte leather surface can be realized. It is preferably present, and more preferably 4.0 to 10 ⁇ m.
• Ra refers to the "arithmetic average roughness" defined in JIS B0601: 2001, and is measured by a known measuring device (for example, an atomic force microscope, a laser microscope, an electron beam microscope, an optical microscope, etc.). be able to.
• the thickness of the sheet-shaped molded product of the present invention is not particularly limited, and is preferably 0.1 to 10 mm, more preferably 0.2 to 5 mm.
• the swelling rate of the sheet-shaped molded product is preferably 0 to 450%, more preferably 0 to 100%, for the reason that the water resistance is better.
• the mass reduction rate of the sheet-shaped molded product is preferably 0 to 15%, more preferably 0 to 8%, for the reason that the water resistance becomes better.
• the mass reduction rate can be obtained by immersing the sheet-shaped molded product in water for 24 hours, drying it at room temperature (23 ° C.) for 48 hours, and then using the following formula.
• Mass reduction rate (%) (mass before immersion-dry mass after immersion) / mass before immersion ⁇ 100 The higher the mass reduction rate, the higher the elution of the plasticizer and therefore the lower the water resistance, and the lower the mass reduction rate, the smaller the elution of the plasticizer and the higher the water resistance.
• the initial elastic modulus of the sheet-shaped molded product is preferably 15 to 60 MPa, more preferably 25 to 55 MPa, because it is excellent in processability.
• the initial elastic modulus is determined by cutting a sheet that has been humidity-controlled for 24 hours under the condition of 25 ° C. and 50% RH into a width of 5 mm and a length of 70 mm using a constant-speed extension type tensile tester, and has a chuck-to-chuck distance of 30 mm and a tensile speed. It is possible to measure at 30 mm / min, create an SS curve, and calculate the elastic modulus (unit: MPa) at the point of maximum inclination at the very initial stage. The higher the initial elastic modulus, the harder it is and the more difficult it is to deform, and the lower the initial elastic modulus, the softer it is and the easier it is to deform.
• the above-mentioned composition of the present invention is applied to form a coating film, and after the coating step, the coating film is dried to form a sheet-shaped molded product. It is a manufacturing method having a drying step.
• the coating method in the coating step is not particularly limited, and examples thereof include a spin coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, and a die coating method.
• the coating amount is preferably adjusted so that a sheet-shaped molded product having a desired thickness can be produced.
• the method for drying the coating film in the drying step is not particularly limited, and examples thereof include methods such as natural drying, blast drying, hot air drying, UV drying, hot roll drying, and infrared drying.
• the artificial leather of the present invention is an artificial leather containing a nonwoven fabric and a polypeptide, a fibrous substance other than the polypeptide and a plasticizer applied to the nonwoven fabric using the composition of the present invention described above.
• the method of applying the polypeptide, the fibrous substance other than the polypeptide and the plasticizer to the nonwoven fabric is not particularly limited, and the present invention includes, for example, a coating step and a drying step in the above-mentioned method for producing a sheet-shaped molded product of the present invention. The method can be mentioned.
• Non-woven fabric fibers made of polyester, polypropylene, polyacrylonitrile, polyethylene, polyamide or the like may be used alone or in combination of two or more.
• Examples of the method for producing a nonwoven fabric include an electric field spinning method, a composite melt spinning method, a melt blow method, and a CVD (chemical vapor deposition) method, and among them, the electric field spinning method is preferable.
• the coating liquid can be used as a paint, and a leather-like surface can be obtained.
• Example 1 To 100 mL of purified water, 1.25 g of carbon black (NIPEX170, manufactured by Orion Engineering Carbons) was added, and the mixture was stirred with a stirrer with ultrasonic waves for 10 minutes. Next, 15 g of gelatin (manufactured by Wako Pure Chemical Industries, Ltd.) as a polypeptide was added to this solution, and the mixture was heated and stirred at 90 ° C. to dissolve it.
• carbon black NIPEX170, manufactured by Orion Engineering Carbons
• 0 g (Mori Machinery, CellFiMC-100), 0.015 g of antibacterial agent (Bauer bottles GmbH, MORTANOL30), and 0.45 g of tanning agent as a cross-linking agent (SILVA, Blancotan CAT).
• SILVA Tinotan CAT
• Example 2 Same as Example 1 except that 20 g of a 5% aqueous solution of cellulose nanofibers was changed to 50 g of a 2% aqueous solution of cellulose nanofibers manufactured by Sugino Machine (BiNFi-s IMa-1002) and 100 mL of purified water was changed to 70 mL of purified water. A sheet-shaped molded body was produced.
• Example 3 Same as Example 1 except that 20 g of a 5% aqueous solution of cellulose nanofibers was changed to 50 g of a 2% aqueous solution of cellulose nanofibers (BiNFi-s WMa-1002) manufactured by Sugino Machine Limited, and 100 mL of purified water was changed to 70 mL of purified water. A sheet-shaped molded body was produced.
• Example 4 Performed except that 15 g of gelatin was changed to a mixture of 13.5 g of gelatin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1.5 g of genetically modified protein (manufactured by Fujifilm, cellnest human type I collagen-like recombinant peptide). A sheet-shaped molded body was produced in the same manner as in Example 1.
• Example 5 The coating liquid 1 was applied to a non-woven fabric (manufactured by Toray, ECS-DCG-KN made of genuine leather) and air-dried at 25 ° C. and 50% RH for 7 days to prepare a sheet-shaped molded product.
• a non-woven fabric manufactured by Toray, ECS-DCG-KN made of genuine leather
• Example 6 Same as Example 1 except that 20 g of a 5% aqueous solution of cellulose nanofibers was changed to 50 g of a 2% aqueous solution of cellulose nanofibers (BiNFi-s FMa-1002) manufactured by Sugino Machine Limited, and 100 mL of purified water was changed to 70 mL of purified water. A sheet-shaped molded body was produced.
• Example 7 Example 1 except that 20 g of a 5% cellulose nanofiber aqueous solution was changed to 100 g of TEMPO oxidized cellulose nanofiber 1% dispersion "Serenpia TC-01A" manufactured by Nippon Paper Co., Ltd., and 100 mL of purified water was changed to 50 mL of purified water. In the same manner as above, a sheet-shaped molded body was produced.
• Example 8 20 g of a 5% aqueous solution of cellulose nanofibers was changed to 50 g of a 2% aqueous solution of cellulose nanofibers manufactured by Sugino Machine (BiNFi-s AMa-1002), and 100 mL of purified water was changed to 70 mL of purified water in the same manner as in Example 1. A sheet-shaped molded body was produced.
• Example 1 A sheet-shaped molded product was produced in the same manner as in Example 1 except that a 5% aqueous solution of cellulose nanofibers was not added.
• Example 2 A sheet-shaped molded product was produced in the same manner as in Example 1 except that 1 g of cellulose fine particles (CELLLULOBEADS D-5, manufactured by DAITO KASEI) was added instead of the 5% aqueous solution of cellulose nanofibers.
• Example 1 From the comparison between Examples 1 to 4 and Example 8, it was found that when the aspect ratio of the fibrous compound is 100 or more, a more excellent matte leather surface can be realized. Further, from the comparison between Example 1 and Example 4, it was found that when a genetically modified protein is used as a part of the polypeptide, a more excellent matte leather surface can be realized. Further, from the comparison between Example 1 and Example 5, it was found that when a polypeptide, a fibrous substance and a plasticizer were added to the nonwoven fabric, a more excellent matte leather surface could be realized, which is suitable as artificial leather. It turned out to be.
• Example 9 0.45 g of a tanning agent as a cross-linking agent is abbreviated as 1,3-bis (vinylsulfonylacetamide) propane (manufactured by Fujifilm, VS-C) [in Table 2 below, "vinyl sulfone”. ], A sheet-shaped molded product was produced in the same manner as in Example 1.
• Example 10 0.45 g of tanning agent as a cross-linking agent, 0.34 g of 1,2-bis (vinylsulfonylacetamide) ethane (manufactured by Fujifilm, VS-B) and 1,3-bis (vinylsulfonylacetamide) propane (Fuji) Mixture with 0.11 g (VS-C) manufactured by Film Co., Ltd. [In Table 2 below, it is abbreviated as "vinyl sulfone mixture”. ], A sheet-shaped molded product was produced in the same manner as in Example 1.
• Example 11 0.45 g of tanning agent as a cross-linking agent is abbreviated as 2,4-dichloro-hydroxy-1,3,5-triazine monosodium [in Table 2 below, "triazine”. ] A sheet-shaped molded product was produced in the same manner as in Example 1 except that the weight was changed to 0.45 g.
• Example 12 A sheet-shaped molded product was produced in the same manner as in Example 9 except that 10.0 g of glycerol as a plasticizer was changed to 10.0 g of diglycerol (diglycerin 801 manufactured by Sakamoto Pharmaceutical Co., Ltd.).
• Example 13 A sheet-shaped molded product was produced in the same manner as in Example 9 except that 10.0 g of glycerol as a plasticizer was changed to 10.0 g of triglycerol (PGL-S manufactured by Sakamoto Pharmaceutical Co., Ltd.).
• Example 14 A sheet-shaped molded product was produced in the same manner as in Example 9 except that 10.0 g of glycerol as a plasticizer was changed to 10.0 g of polyglycerol (polyglycerin # 500 manufactured by Sakamoto Pharmaceutical Co., Ltd.).
• Example 15 A sheet-shaped molded product was produced in the same manner as in Example 9 except that 10.0 g of glycerol as a plasticizer was changed to 10.0 g of tritryl phosphate (manufactured by Wako Pure Chemical Industries, Ltd.).
• Example 16 A sheet-shaped molded product was produced in the same manner as in Example 9 except that 10.0 g of glycerol as a plasticizer was changed to 10.0 g of dibutyl phthalate (manufactured by Wako Pure Chemical Industries, Ltd.).
• Example 17 A sheet-like molded product was naturally dried at 25 ° C. and 50% RH for 7 days in the same manner as in Example 12 except that the coating liquid was applied to the non-woven fabric (Toray Industries, Ltd., ECS-DCG-KN made of genuine leather). Was produced.

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• 2021
  • 2021-05-20 CN CN202180037386.1A patent/CN115698422A/zh active Pending
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